Photovoltaic (PV)-powered alkaline electrolyzer system (PVPAES) is an advanced technique to convert the off-grid and intermittent PV-based solar energy into storable and transportable electrolyzer-based hydrogen energy with zero carbon emissions. However, it is difficult to realize the coordinated control of the off-grid PV module and the alkaline electrolyzer, due to the multiple timescale dynamics. To address this challenge, the PVPAES is decomposed into the slow part and fast part based on the dynamic time scale. Exploiting the decomposed subsystems, the slow one is assumed to be managed well by the auxiliary controller. For the fast one, a centralized economic model predictive control (CEMPC) scheme is constituted. This CEMPC integrates the energy management system and local feedback control into a single optimal control framework. A mathematical model of the PVPAES is established, on the basis of which the CEMPC directly adopts the economic indices as the cost function to realize the flexible power point tracking, power supply-demand balance, and dynamic economic optimization. Moreover, the inherent strong nonlinearity of PVPAES results in the nonconvex mixed-integer nonlinear programming optimization problem in the CEMPC. The exhaustive search algorithm utilizing finite converter switching states is adopted to achieve the global economic optimum. The effectiveness of the proposed CEMPC controller is illustrated through simulations under varying irradiance conditions.